CN103329334B - Nonaqueous electrolyte battery - Google Patents

Nonaqueous electrolyte battery Download PDF

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Publication number
CN103329334B
CN103329334B CN201280005819.6A CN201280005819A CN103329334B CN 103329334 B CN103329334 B CN 103329334B CN 201280005819 A CN201280005819 A CN 201280005819A CN 103329334 B CN103329334 B CN 103329334B
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solid electrolyte
powder
negative electrode
battery
electrode layer
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CN103329334A (en
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后藤和宏
上村卓
吉田健太郎
竹山知阳
神田良子
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a kind of nonaqueous electrolyte battery, this nonaqueous electrolyte battery has high power capacity and high volumetric power density, and can have the charge/discharge cycle characteristics of enhancing.The solid electrolyte layer that described nonaqueous electrolyte battery comprises anode layer, negative electrode layer and arranges between, the layers.Described negative electrode layer contains the powder of negative active core-shell material and the powder of solid electrolyte.In described negative active core-shell material, discharge and recharge volume change is less than 1%, and the average grain diameter of described powder is less than 8 μm.Described solid electrolyte layer is formed by vapor phase method.During described discharge and recharge, volume change is that the example of the negative active core-shell material of less than 1% comprises Li 4ti 5o 12not graphitisable carbon.

Description

Nonaqueous electrolyte battery
Technical field
The present invention relates to nonaqueous electrolyte battery, the solid electrolyte layer that this nonaqueous electrolyte battery comprises anode layer, negative electrode layer and is arranged between these layers.
Background technology
Nonaqueous electrolyte battery has long-life, high efficiency and high power capacity, and for portable equipments such as portable phone, notebook computer and digital cameras.The representative example of this nonaqueous electrolyte battery comprises lithium battery and lithium rechargeable battery (hereinafter referred to as " lithium-base battery "), and it utilizes giving of the lithium ion between anode layer and negative electrode layer and acceptable response.
The dielectric substrate that this lithium-base battery comprises the anode layer containing positive electrode active materials, the negative electrode layer containing negative active core-shell material and is arranged between these layers.Secondary cell shifts to carry out charging and discharging through dielectric substrate by lithium (Li) ion anode layer and negative electrode layer.In addition, the all-solid-state battery (such as, referenced patent document 1 to 3) using inorganic solid electrolyte to replace organic electrolyte is proposed recent years.
About manufacturing the technology of all-solid-state battery, patent documentation 1 set forth and positive electrode active material powder, electrolyte powder and negative active core-shell material powder to be encased in predetermined mould and to suppress.On the other hand, patent documentation 2 and 3 set forth by vapor phase method by anode layer, solid electrolyte layer and negative electrode layer successively film forming, thus it is stacked together.
Patent documentation 3 also discloses the use of negative active core-shell material, and this negative active core-shell material is material with carbon element such as (such as) graphite or hard carbon etc., silicon (Si), silica (SiO x(0<x<2)), ashbury metal, lithium nitride cobalt (LiCoN), Li metal or lithium alloy (as LiAl) (the 0050th section of patent documentation 3).
Reference listing
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication No.2001-273928
Patent documentation 2: Japanese Unexamined Patent Application Publication No.2009-199920
Patent documentation 3: Japanese Unexamined Patent Application Publication No.2004-335455
Summary of the invention
Technical problem
But, be difficult to the capacity of existing all solid state nonaqueous electrolyte battery (lithium-base battery) and volumetric power density (power density of per unit volume) are all improved.
Such as, when the powder-type described in patent documentation 1 (wherein all component parts, namely anode layer, solid electrolyte layer and negative electrode layer, all formed by powder forming), anode layer and negative electrode layer have large thickness, thus are easy to guarantee capacity; But solid electrolyte layer also has large thickness, thus volumetric power density is caused to decline.On the other hand, (wherein all component parts when the film-forming type described in patent documentation 2 and 3, namely anode layer, solid electrolyte layer and negative electrode layer, be all formed as film by vapor phase method), this solid electrolyte layer has little thickness thus is easy to guarantee volumetric power density; But this anode layer and negative electrode layer also have little thickness, thus capacity is caused to reduce.
The present invention has been carried out based on above-mentioned situation.The object of the present invention is to provide a kind of nonaqueous electrolyte battery, this nonaqueous electrolyte battery has high power capacity and high volumetric power density, and can have the charge and discharge cycles ability of enhancing.
The solution of problem
The present inventor conducts in-depth research and thus finds following result.
The present inventor thinks and forms negative electrode layer by powder forming and by vapor phase method, solid electrolyte layer be formed as film, can improve capacity and the volumetric power density of battery simultaneously.Like this, in fact manufactured all solid state nonaqueous electrolyte battery by following method, the method is: prepare positive pole parts, wherein LiCoO 2powder compact serves as anode layer, and in this anode layer, forms membranaceous solid electrolyte layer by vapor phase method; And prepare anode member, wherein powdered graphite formed body serves as negative electrode layer, and on this negative electrode layer, forms membranaceous solid electrolyte layer by vapor phase method; Arrange these parts in the mode contacted with each other, the solid electrolyte layer making these parts is toward each other and by these part bonding to together.Charge and discharge cycles test is carried out to this battery.Consequently, in the cell, there occurs internal short-circuit in the starting stage of loop test, and find that this battery has problems in charge and discharge cycles ability.This may be that stress produced thus causes creating crackle in solid electrolyte layer because negative electrode layer there occurs expansion and shrinks in charge and discharge process; Li on negative electrode layer surface is deposited on dendritic growth in the charge and discharge process repeated, thus through this crackle; Li skeleton arrives anode layer and causes internal short-circuit.In addition, in charge and discharge process negative electrode layer expansion and shrink adhesion strength may to be caused between negative electrode layer and solid electrolyte layer to reduce.In this case, the Li ionic transfer resistance at interface layer place may increase, thus causes the decline of charge and discharge cycles ability.
The present inventor has found the above results and has completed the present invention.
(1) the nonaqueous electrolyte battery according to the present invention solid electrolyte layer that comprises anode layer, negative electrode layer and be arranged between these layers.Described negative electrode layer contains the powder of negative active core-shell material and the powder of solid electrolyte.In negative active core-shell material, discharge and recharge volume change is less than 1%, and the average grain diameter of powder is less than 8 μm.Described solid electrolyte layer is formed by vapor phase method.
In this is formed, negative electrode layer is formed by powder forming, and solid electrolyte layer is formed as film by vapor phase method.Capacity and volumetric power density can be made thus to be all improved.
When the discharge and recharge volume change of negative active core-shell material is less than 1%, in charge and discharge process negative electrode layer expansion and shrink and can be inhibited, and in solid electrolyte layer, the reduction of the generation of crackle and the adhesion strength between negative electrode layer and solid electrolyte layer also can be inhibited.This discharge and recharge volume change (%) refers to the value ([Vc-Vd]/Vd) represented with percentage, the volume (Vd) when the volume (Vc) when this value is by being embedded by Li under fully charged state (reaching state during end of charge voltage) deducts that Li discharges under full discharge condition (reaching state during final discharging voltage) volume (Vd) when being discharged divided by Li under full discharge condition by the volume change of gained and obtain.Therefore, internal short-circuit is less likely to occur and can realizes the enhancing of charge and discharge cycles ability.
In the present invention, negative electrode layer comprises the powder of negative active core-shell material and the powder of solid electrolyte.Therefore, negative electrode layer has wherein solid electrolyte and is present in the circumgranular structure of negative active core-shell material.When negative active core-shell material has different-grain diameter, even if when these materials have identical volume change, the material with greater particle size still has the absolute magnitude of larger change in volume.Therefore, when the powder of negative active core-shell material has the average grain diameter of less than 8 μm, the absolute magnitude of the change in volume of this negative active core-shell material particle is little.Like this, in charge and discharge process, the expansion and shrinking of negative electrode layer just can be effectively suppressed, and in solid electrolyte layer, the decline of the generation of crackle and the adhesion strength between negative electrode layer and solid electrolyte layer also can be inhibited.In addition, when the average grain diameter of the powder of negative active core-shell material is below 8 μm, the negative electrode layer of shaping has low surface roughness, therefore also easily on negative electrode layer, forms solid electrolyte layer (film forming) by vapor phase method.Preferably, the average grain diameter of the powder of negative active core-shell material is (such as) less than 1 μm, thus the volume change of particle diminishes, and the surface roughness of negative electrode layer also step-down.
As mentioned above, negative active core-shell material there occurs the change (expand and shrink) of volume in charge and discharge process, and therefore strictly speaking, in charge and discharge process, the average grain diameter of powder also there occurs change.But in the present invention, the volume change due to negative active core-shell material is less than 1%, so the average grain diameter of powder there is no change.The average grain diameter of negative active core-shell material powder contained in negative electrode layer is substantially identical with the average grain diameter of material powder to be formed.Particle diameter is determined under the state (namely in discharge condition) that negative active core-shell material has discharged Li.Here, average grain diameter refers to the average grain diameter (arithmetic mean of the particle diameter captured by optical microscopy or transmission electron microscopy) that defined by Japanese Industrial Standards (JIS) Z8901:2006.
From guaranteeing that the angle of capacity is considered, the thickness of negative electrode layer is preferably (such as) more than 30 μm, is more preferably more than 60 μm.In the present invention, because negative electrode layer is formed by powder forming, so with formed the situation of film by vapor phase method compared with, easily form the negative electrode layer with this large thickness.On the other hand, from guaranteeing that the angle of volumetric power density is considered, the thickness of solid electrolyte layer is preferably (such as) less than 30 μm, is more preferably less than 10 μm.In the present invention, because solid electrolyte layer is formed as film by vapor phase method, therefore compared with the situation of powder forming, easily form the solid electrolyte layer with this little thickness.In addition, compared with the situation of powder forming, it is fine and close for being formed as membranaceous solid electrolyte layer by vapor phase method, is therefore difficult to the internal short-circuit occurring to cause due to the growth of Li skeleton.
The example of vapor phase method comprises physical vapor deposition (PVD) method, as vacuum deposition method, pulsed laser deposition (PLD) method, laser ablation method, ion plating method and sputtering method etc.The condition of vapor phase method has no particular limits.But in film forming room's atmosphere, the concentration of impurity is lower in film forming procedure, gained film is finer and close.Therefore, before beginning film forming, the vacuum degree in film forming room is preferably set to below 0.002Pa.
In addition, in the present invention, the interface between negative electrode layer and solid electrolyte layer is carried out giving of Li ion and is accepted.Here, when negative electrode layer is only formed by negative active core-shell material powder, ion give and acceptance is understood and be carried out smoothly in negative electrode layer interface.But, may following problems be there is: ion does not spread fully in the inside (with the part of interfacial separation) of negative electrode layer, and the negative active core-shell material powder of negative electrode layer inside is not effectively used to cell reaction.When the thickness of negative electrode layer increases (e.g., more than 20 μm), this problem can become more serious.For this reason, negative electrode layer comprises the powder of negative active core-shell material and the powder of solid electrolyte; The powder of negative active core-shell material and the powder of solid electrolyte mix in negative electrode layer.Like this, solid electrolyte powder facilitates the diffusion of ion in negative electrode layer inside, thus the negative active core-shell material powder of negative electrode layer inside can be effectively used to cell reaction.Internal resistance can be reduced thus.
(2) according in the nonaqueous electrolyte battery of embodiment of the present invention, negative active core-shell material is Li 4ti 5o 12or not graphitisable carbon (hard carbon).
Preferred Li 4ti 5o 12or hard carbon (not graphitisable carbon) is because its discharge and recharge volume change is less than 1%.In such negative active core-shell material, the embedding of Li when entering the interstitial site of lattice by Li ion thus realize charging; And the release of Li when departing from by Li ion from the interstitial site of lattice thus realize electric discharge.Therefore, with (such as) Li metal, Li alloy and compared with Li alloyed metal (AM), the volume change of discharge and recharge is low.In addition, with graphite-phase usually used ratio, the volume change of discharge and recharge is also low.Along band it is mentioned that, the discharge and recharge volume change of graphite is about 10%.When with Li metal or Li alloy as negative active core-shell material time, on the surface that Li is deposited on negative electrode layer and often with dendritic growth.
(3) according in the nonaqueous electrolyte battery of embodiment of the present invention, the solid electrolyte be included in negative electrode layer is sulfide-based solid electrolyte.
Usually, solid electrolyte is for containing Li 2the sulfide-based solid electrolyte of S and Li 3pO 4, the oxide based solid electrolyte such as LiPON.Sulfide-based solid electrolyte (such as) is like this Li 2s-P 2s 5be electrolyte, Li 2s-SiS 2be electrolyte or Li 2s-B 2s 3be electrolyte, and can P be contained 2o 5or Li 3pO 4.Preferred sulfide-based solid electrolyte is because they have the lithium-ion-conducting higher than oxide based solid electrolyte usually.Especially, in sulfide-based solid electrolyte, more preferably there is the conductive Li of high-lithium ion 2s-P 2s 5it is solid electrolyte.
Negative electrode layer containing negative active core-shell material powder and solid electrolyte powder optionally can also contain conductive auxiliary agent or binding agent.Here, when solid electrolyte contained in negative electrode layer is sulfide-based solid electrolyte, this sulfide-based solid electrolyte is softer than oxide based solid electrolyte, and has high deformability, is therefore easy to the function demonstrating binding agent.The example of conductive auxiliary agent comprises the carbon black such as acetylene black (AB) and Ketjen black (KB).The example of binding agent comprises polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF).
(4) according in the nonaqueous electrolyte battery of embodiment of the present invention, the content of the powder of the negative active core-shell material in negative electrode layer is more than 30 quality % and below 80 quality %.
When in negative electrode layer, the content of negative active core-shell material powder is less than 30 quality %, negative active core-shell material is low relative to the ratio of whole negative electrode layer, thus capacity may step-down.On the other hand, when in negative electrode layer, the content of negative active core-shell material powder is greater than 80 quality %, the corresponding reduction of ratio regular meeting of solid electrolyte powder etc.Therefore, interior resistance may uprise, or adhesive property may be deteriorated.About the ratio of negative active core-shell material powder and solid electrolyte powder in negative electrode layer, such as, the ratio of negative active core-shell material powder can be 30 quality % to 80 quality %, and the ratio of solid electrolyte powder can be 20 quality % to 70 quality %.For the content of negative active core-shell material powder in negative electrode layer, its lower limit is more preferably and is greater than 30 quality %, is more preferably more than 40 quality % further; And its upper limit is more preferably and is less than 80 quality %, is more preferably below 70 quality % further.
(5) according in the nonaqueous electrolyte battery of embodiment of the present invention, solid electrolyte layer contains sulfide-based solid electrolyte.
As mentioned above, preferred sulfide-based solid electrolyte is because it has the lithium-ion-conducting higher than oxide based solid electrolyte usually.Especially, more preferably there is the conductive Li of high-lithium ion 2s-P 2s 5it is solid electrolyte.
Anode layer contains positive electrode active materials.The example of positive electrode active materials comprises the composite oxides containing lithium, such as LiCoO 2, LiNiO 2, LiMn 2o 4, LiFePO 4, LiNi 1/3co 1/3mn 1/3o 2and LiNi 0.8co 0.15al 0.05o 2.Especially, in these positive electrode active materials, preferably LiNi 1/3co 1/3mn 1/3o 2and LiNi 0.8co 0.15al 0.05o 2, its discharge and recharge volume change is less than 1%.Along band it is mentioned that, LiCoO usually used 2discharge and recharge volume change be 2.6%.When anode layer as negative electrode layer be formed by pressed powder time, preferably use average grain diameter to be the positive electrode active material powder of less than 6 μm.
In nonaqueous electrolyte battery according to embodiments of the present invention, the boundary layer of the interface resistance reduced between these two layers can be set between anode layer and solid electrolyte layer.Such as, when using oxide as positive electrode active materials and when using sulfide as solid electrolyte, may reacting between this oxide and sulfide, the interface resistance at the interface between anode layer and solid electrolyte layer is caused to increase.Based on this reason, can arrange such boundary layer, this boundary layer inhibits two interlayers mutually to spread in the nearly interface zone of anode layer and solid electrolyte interlayer, thus inhibits reaction.Interface resistance can be reduced thus.Example for the formation of the material of boundary layer comprises LiNbO 3, LiTaO 3, Li 4ti 5o 12, Li xla (2-X)/3tiO 3(X=0.1 to 0.5), Li 7+Xla 3zr 2o 12+ (X/2)(-5≤X≤3), Li 3.6si 0.6p 0.4o 4, Li 1.3al 0.3ti 1.7(PO 4) 3, Li 1.8cr 0.8ti 1.2 (pO 4) 3and Li 1.4in 0.4ti 1.6(PO 4) 3.These materials can be used alone or two or more combinationally uses.
Negative electrode layer is by the powder of negative active core-shell material, the powder of solid electrolyte and optional conductive auxiliary agent or binding agent being mixed, and the formed body suppressed this mixture of powders and obtain.When suppressing, institute's applied pressure is preferably 100MPa to 600MPa.After compressing, can heat-treat.In this case, heating-up temperature is preferably 120 DEG C to 250 DEG C.
The same with solid electrolyte layer, anode layer and above-mentioned boundary layer can be formed by vapor phase method.Or, the same with negative electrode layer, anode layer can be formed through compacting positive electrode active material powder and the formed body that obtains; Or anode layer can be formed by damp process (rubbing method) such as (such as) sol-gal process, colloid method or castings.When anode layer is equally formed as the formed body of positive electrode active material powder with negative electrode layer, this powder preferably mixes with solid electrolyte powder, and optionally adds conductive auxiliary agent or binding agent.In this case, about the ratio of positive electrode active material powder in anode layer and solid electrolyte powder, such as, the ratio of positive electrode active material powder can be 50 quality % to 90 quality %, and the ratio of solid electrolyte powder can be 10 quality % to 50 quality %.Solid electrolyte powder is preferably sulfide-based solid electrolyte powder.Beneficial effect of the present invention
In nonaqueous electrolyte battery according to the present invention, negative electrode layer is formed by powder forming; Solid electrolyte layer is formed as film by vapor phase method; And negative active core-shell material has the discharge and recharge volume change of less than 1%.Thus, battery can have the charge and discharge cycles ability of high power capacity, high volumetric power density and enhancing.
Embodiment
(embodiment 1)
Manufacture according to nonaqueous electrolyte battery of the present invention (lithium-base battery), and its battery performance has been evaluated.
[manufacture of battery]
By Li 4ti 5o 12powder (average grain diameter: 1 μm) and Li 2s-P 2s 5be that solid electrolyte powder (average grain diameter: 1 μm to 5 μm) prepares negative electrode mix with the mixing of the mass ratio of 50:50.Then, stainless steel (SUS) the 316L paper tinsel (thickness: 10 μm) serving as negative electrode collector is placed in mould, and negative electrode mix is filled on paper tinsel.Then carry out compressing to this paper tinsel and negative electrode mix under the pressure of 360MPa.So just, prepared anode member, in this anode member, negative electrode layer (Li 4ti 5o 12and Li 2s-P 2s 5be the formed body of solid electrolyte) be formed on negative electrode collector.In this anode member, the thickness of negative electrode layer is 60 μm.Li 2s-P 2s 5to be solid electrolyte be by being the Li of 4:1 to mol ratio 2s and P 2s 5carry out ball milling mixing, be prepared by the heat treatment then carried out in Ar atmosphere one hour at 240 DEG C.
By LiCoO 2powder (average grain diameter: 10 μm) and Li 2s-P 2s 5be that solid electrolyte powder (average grain diameter: 1 μm to 5 μm) prepares cathode mix with the mixing of the mass ratio of 70:30.Then, the SUS316L paper tinsel (thickness: 20 μm) serving as positive electrode collector is placed in mould, and cathode mix is filled on paper tinsel.Then carry out compressing to this paper tinsel and cathode mix under the pressure of 360MPa.So just, prepared positive pole parts, in these positive pole parts, anode layer (LiCoO 2and Li 2s-P 2s 5be the formed body of solid electrolyte) be formed on positive electrode collector.In these positive pole parts, the thickness of anode layer is 70 μm.Li 2s-P 2s 5to be solid electrolyte be by being the Li of 4:1 to mol ratio 2s and P 2s 5carry out ball milling mixing, be prepared by the heat treatment then carried out in Ar atmosphere one hour at 240 DEG C.
Subsequently, on the negative electrode layer of anode member and in the anode layer of positive pole parts, Li is formed by PLD method 2s-P 2s 5be the film of solid electrolyte, thus define solid electrolyte layer (thickness: 5 μm).This Li 2s-P 2s 5to be the film of solid electrolyte be by mol ratio is the Li of 4:1 2s and P 2s 5mixture formed.
Such layout positive pole parts and anode member, these two parts are contacted with each other and the solid electrolyte layer making two parts toward each other.Applying the pressure of 16MPa along arranged direction and under the condition heated at 190 DEG C, these two parts kept 130 minutes.Consequently, solid electrolyte layer is fused together thus by part bonding to together.So just, obtained battery.
The nonaqueous electrolyte battery so manufactured is included in charge-discharge test unit.Be No.1-1 by this sample identity.
Manufacture battery according to sample No.1-1, difference is: in the manufacture process of anode member, replaces Li with powdered graphite (average grain diameter: 5 μm) 4ti 5o 12powder.This battery is included in charge-discharge test unit.Be No.1-2 by this sample identity.
Manufacture battery according to sample No.1-1, difference is: in the manufacture process of positive pole parts, with LiNi 0.8co 0.15al 0.05o 2powder (average grain diameter: 6 μm) replaces LiCoO 2powder.This battery is included in charge-discharge test unit.Be No.1-3 by this sample identity.
[evaluation of battery]
The formation of manufactured battery as shown in Table I.To the evaluation that the battery manufactured carries out below.Result as shown in Table II.
< charge and discharge cycles ability (capability retention) >
Carry out charge and discharge cycles test to check charge and discharge cycles ability (capability retention), in charge and discharge cycles test, a discharge and recharge is defined as a circulation.Charge and discharge cycles test is carried out under the following conditions: room temperature (about 25 DEG C); When negative active core-shell material is Li 4ti 5o 12time, cut-ff voltage (final discharging voltage is to end of charge voltage) is 1.0V to 3.5V; When negative active core-shell material is graphite, cut-ff voltage is 3.0V to 4.2V; Further, in above-mentioned two situations, electric current is all at 50 μ A/cm 2current density (id) under constant.By the discharge capacity of the 50th circulation time divided by first time circulation time initial discharge capacity thus obtain capability retention.The initial discharge capacity of each battery and capability retention are as shown in Table II.
< negative pole utilance >
Initial discharge capacity in being tested by above-mentioned charge and discharge cycles is determined at 50 μ A/cm 2current density under the utilance of negative pole.In addition, under above-mentioned test condition, be 300 μ A/cm by current density 2constant current under initial discharge capacity determine that current density is 300 μ A/cm 2time negative pole utilance.It should be noted that and discharge capacity is obtained utilance divided by the theoretical capacity of negative pole.The theoretical capacity of negative pole is the product of the volume of negative active core-shell material contained in the theoretical capacity of the per unit volume of negative active core-shell material and negative electrode layer.At current density (id=50 μ A/cm 2with 300 μ A/cm 2) under each battery negative pole utilance as shown in Table II.
< leads and compares >
Be 50 μ A/cm by current density 2constant current time initial discharge capacity and current density be 300 μ A/cm 2constant current time initial discharge capacity determine rate ratio.The rate that it should be noted that is 300 μ A/cm than by current density 2time discharge capacity be 50 μ A/cm divided by current density 2time discharge capacity and obtain.The rate ratio of battery as shown in Table II.
Resistance > in <
In first circulation that above-mentioned charge and discharge cycles is tested, under the fully charged state realized by charging to end of charge voltage, with 50 μ A/cm 2constant current start electric discharge.From electric discharge after predetermined time, measure discharge voltage and measure interior resistance.It should be noted that and end of charge voltage is deducted this discharge voltage, by gained voltage divided by 2, then by income value divided by 50 μ A/cm 2, thus obtain interior resistance.The interior resistance of battery as shown in Table II.
[Table I]
[Table II]
Result proves, the battery of sample No.1-1 and No.1-3 stably can run more than 50 circulations and internal short-circuit can not occur.In addition, about the discharge capacitance (for the initial discharge capacity of first time circulation time) of the 50th circulation time, the battery of sample No.1-1 is 95%, and the battery of sample No.1-3 is 97%.Especially, the battery of sample No.1-3 has the high discharge capacitance of more than 96% at the 50th circulation time, finds that its charge and discharge cycles ability is excellent.In addition, in the battery of sample No.1-1 and No.1-3, initial discharge capacity is 2mAh/cm 2above; Be 50 μ A/cm in current density 2with 300 μ A/cm 2time negative pole utilance be more than 80%; Rate ratio is more than 80%; And interior resistance is less than 100 Ω cm 2.Under contrast, in the battery of sample No.1-2, observe the phenomenon that can not be charged to 4.2V at the 24th circulation time; Probably there occurs internal short-circuit.
(embodiment 2)
Manufacture the battery changing the average grain diameter of negative active core-shell material powder, and its battery performance has been evaluated.
Manufacture battery according to sample No.1-3, difference is: in the manufacture process of anode member, by Li 4ti 5o 12the average grain diameter of powder changes 8 μm and 20 μm into.These batteries are included in charge-discharge test unit.Be No.2-1 and 2-2 by these sample identity.
The formation of manufactured battery as shown in Table III.The method identical according to embodiment 1 is evaluated manufactured battery.Result as shown in Table IV.
[Table III]
[Table IV]
Consequently, compared with the battery of the sample No.2-2 of coarse with negative active core-shell material powder (average grain diameter: 20 μm), the battery of the sample No.2-1 of powder comparatively thin (average grain diameter: 8 μm) is more than 96% at the discharge capacitance of the 50th circulation time, finds that its charge and discharge cycles ability is excellent.In addition, in the battery of sample No.2-1, initial discharge capacity is 2mAh/cm 2above; Be 50 μ A/cm in current density 2with 300 μ A/cm 2time negative pole utilance be more than 80%; Rate ratio is more than 80%; And interior resistance is less than 100 Ω cm 2.Therefore find, its capacity is high, and rate specific characteristic is excellent, and interior resistance is low.Compared with the battery of sample No.2-1, in the battery of sample No.2-2, find that (current density is 300 μ A/cm to high electric current 2) under negative pole utilance be less than 80% low value, and find that its rate specific characteristic is poor.In addition, find that the battery of sample No.2-2 has 100 Ω cm 2resistance in above height.
(embodiment 3)
The battery that the content having manufactured negative active core-shell material powder in negative electrode layer changes within the scope of 30 quality % to 80 quality %, and its battery performance is evaluated.
Manufacture battery according to sample No.1-3, difference is: in the manufacture process of anode member, by Li 4ti 5o 12the content of powder becomes 30 quality %, 40 quality %, 70 quality % and 80 quality %.It should be noted that negative electrode layer has following thickness to provide relative to the overall identical theoretical capacity of each negative electrode layer: during 30 quality %, thickness is 280 μm; During 40 quality %, thickness is 200 μm; During 70 quality %, thickness is 100 μm; And during 80 quality %, thickness is 80 μm.These batteries are included in charge-discharge test unit.Be No.3-1,3-2,3-3 and 3-4 by these sample identity.
The formation of manufactured battery as shown in Table V.The method identical according to embodiment 1 is evaluated manufactured battery.Result as shown in Table VI.
[Table V]
[Table VI]
Consequently, the battery of sample No.3-1 to 3-4 is more than 96% at the discharge capacitance of the 50th circulation time, finds that it has excellent charge and discharge cycles ability.Especially, be respectively in the battery of sample No.3-2 and 3-3 of 40 quality % and 70 quality % at the content of negative active core-shell material, initial discharge capacity is 2mAh/cm 2above; Be 50 μ A/cm in current density 2with 300 μ A/cm 2time negative pole utilance be more than 80%; Rate ratio is more than 80%; And interior resistance is less than 100 Ω cm 2.Thus find that its capacity is high, rate specific characteristic is excellent and interior resistance is low.Under contrast, be respectively in the battery of sample No.3-1 and 3-4 of 30 quality % and 80 quality % at the content of negative active core-shell material, its internal resistance is 100 Ω cm 2above high level.Especially, in the battery of sample No.3-4, initial discharge capacity is less than 2mAh/cm 2; Be 50 μ A/cm in current density 2with 300 μ A/cm 2under negative pole utilance be less than 80% low value; And find its capacity and rate specific characteristic poor.
(embodiment 4)
Manufacture the battery changing the raw material of negative active core-shell material, and its battery performance has been evaluated.
Manufacture battery according to sample No.1-3, difference is: in the manufacture process of anode member, replace Li with hard carbon powder (average grain diameter: 5 μm) 4ti 5o 12powder.It should be noted that the thickness of negative electrode layer is 80 μm.This battery is included in charge-discharge test unit.Be No.4-1 by this sample identity.
Manufacture battery according to sample No.4-1, difference is: in the manufacture process of anode member, instead of hard carbon powder with powdered graphite (average grain diameter: 5 μm).This battery is included in charge-discharge test unit.Be No.4-2 by this sample identity.
The formation of manufactured battery as shown in Table VII.According to the method identical with embodiment 1, manufactured battery is evaluated.Result as shown in Table VIII.It should be noted that when negative active core-shell material is hard carbon, the same with the situation of graphite, cut-ff voltage is set to 3.0V to 4.2V.
[Table VII]
[Table VIII]
Result confirms, more than negative active core-shell material 50 circulations that have been the battery stable operation of the sample No.4-1 of hard carbon, and internal short-circuit does not occur.In addition, this battery has the high discharge capacitance of more than 96% at the 50th circulation time, finds that its charge and discharge cycles ability is excellent.And in the battery of sample No.4-1, initial discharge capacity is 2mAh/cm 2above; Be 50 μ A/cm in current density 2with 300 μ A/cm 2time negative pole utilance be more than 80%; Rate ratio is more than 80%; And interior resistance is less than 100 Ω cm 2.Thus find that its capacity is high, rate specific characteristic is excellent and interior resistance is low.Under contrast, be in the battery of sample No.4-2 of graphite at negative active core-shell material, identical with the battery of sample No.1-2, before arrival the 50th circulation, observe the phenomenon that can not be charged to 4.2V; Probably there occurs internal short-circuit.
The above results demonstrates to draw a conclusion.For negative electrode layer, there is low discharge and recharge volume change and by fine particle (such as, Li by using 4ti 5o 12or hard carbon (not graphitisable carbon)) negative active core-shell material that forms, in charge and discharge process negative electrode layer expansion and shrink and can be inhibited and charge and discharge cycles ability can be improved.
In addition, also demonstrate as drawn a conclusion.For anode layer, there is low discharge and recharge volume change (volume change is less than 1%) and positive electrode active materials (such as, the LiNi be made up of fine particle (average grain diameter is less than 6 μm) by using 0.8co 0.15al 0.05o 2), in charge and discharge process anode layer expansion and shrink can be inhibited and charge and discharge cycles ability can be improved further.
The invention is not restricted to above-mentioned embodiment.Suitably modification can be carried out without departing from the spirit and scope of the present invention.
Industrial applicibility
Nonaqueous electrolyte battery according to the present invention can be used for the power supply of (such as) portable phone, notebook computer, digital camera or electric motor car.

Claims (5)

1. a nonaqueous electrolyte battery, the solid electrolyte layer comprising anode layer, negative electrode layer and be arranged between these layers,
Wherein, described negative electrode layer contains the powder of negative active core-shell material and the powder of solid electrolyte,
In described negative active core-shell material, discharge and recharge volume change is less than 1%, and the average grain diameter of described powder is less than 8 μm, and
Described solid electrolyte layer is formed by vapor phase method, and thickness is less than 30 μm.
2. nonaqueous electrolyte battery according to claim 1, wherein, described negative active core-shell material is Li 4ti 5o 12or not graphitisable carbon.
3. nonaqueous electrolyte battery according to claim 1 and 2, wherein, the described solid electrolyte be included in described negative electrode layer is sulfide-based solid electrolyte.
4. nonaqueous electrolyte battery according to claim 1 and 2, wherein, the content of the powder of the described negative active core-shell material in described negative electrode layer is more than 30 quality % and below 80 quality %.
5. nonaqueous electrolyte battery according to claim 1 and 2, wherein, described solid electrolyte layer contains sulfide-based solid electrolyte.
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